CN101954295B - Catalyst system for methanol low-pressure carbonyl synthesis of acetic acid and application thereof - Google Patents
Catalyst system for methanol low-pressure carbonyl synthesis of acetic acid and application thereof Download PDFInfo
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- CN101954295B CN101954295B CN2010102918895A CN201010291889A CN101954295B CN 101954295 B CN101954295 B CN 101954295B CN 2010102918895 A CN2010102918895 A CN 2010102918895A CN 201010291889 A CN201010291889 A CN 201010291889A CN 101954295 B CN101954295 B CN 101954295B
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Abstract
The invention relates to a catalyst system used for methanol low-pressure carbonyl synthesis of acetic acid, which uses rhodium compounds as the active component carbonylation of carbonyl synthesis catalyst and uses alkyl iodide, water, hydroiodic acid, alkali metal iodate and sulfonate as promoters, and uses acetic acid as polar solvent. Because sulfonate is added to the catalyst system, better catalytic activity and stability are achieved. In methanol carbonylation, the catalyst system can convert methanol into acetic acid at high speed with high selectivity under lower temperature and pressure. The reaction reduces the concentration of water and hydroiodic acid, and reduces corrosivity to equipment.
Description
Technical field
The present invention relates to a kind of catalyst system and application thereof that is used for catalysis methanol low pressure carbonyl synthesis acetic acid.
Background technology
The industrialized preparing process of acetic acid has acetaldehyde oxidation, butane or light oil liquid phase oxidation, methanol carbonylation.Low-pressure methanol carbonylation method wherein has that flow process is simple, reaction condition is gentle, selectivity is good, low power consumption and other advantages, has become the most competitive in the world production of acetic acid method at present, also is acetic acid synthesized in the world main production route at present.In addition, material benzenemethanol is in liberal supply and with low cost, and has the atomic economy reaction characteristic that total overall reaction thing molecule generates whole purpose product molecules, when having reduced the accessory substance environmental pollution, the coordinated development of economy and environmental protection is had great significance.
In carbonylation of methanol synthesis process route, the research of catalyst is an important content.Purpose is to study active high, good stability, is easy to reclaim, and has the novel catalyst system of homogeneous phase and heterogeneous two types of catalyst advantages concurrently.Research for many years mainly concentrates on these several aspects of base metal, part, carrier and auxiliary agent, and the purpose of its research is to improve existing activity of such catalysts and stability, reaches the raising reaction rate, increases the purpose of acetic acid productive rate.
Mostly the activated centre that existing industrial carbonylation is produced the acetic acid catalyst system and catalyzing is [Rh (CO)
2I
2]
-, for a long time, further improve [Rh (CO)
2I
2]
-As the stability of catalytic active species in reaction, and reduce the water content in the reaction system, be one of important contents of methanol carbonyl synthesized acetic acid catalyst research, and obtained certain progress.Wherein comparatively effective method is with the little molecule that contains nitrogen, phosphorus, oxygen, sulphur functional group or macromolecule ligand and Rh formation complex, reaches the purpose of improving rhodium active specy stability, improving its catalytic activity.For example, (CN100750, US5281359 US6458996), make catalyst when keeping higher carbonylation activity, and heat endurance also is improved as the part of catalyst to adopt high polymer.
In numerous all kinds of catalyst researches; The selection of reactive metal is except that rhodium; Many transition metal such as iridium, ruthenium, nickel, cobalt are all studied, and certain progress are also arranged, wherein with iridium catalyst system and catalyzing (EP849249; US5672743) best results, the reactivity worth of catalyst has had great improvement.
Adopt metal salt stabilizers to improve the research of rhodium catalyst system and catalyzing performance, also quite become effective.For example; (EP 0161874; JP60-239434) through adding the salt compounded of iodine of high level alkali metal (lithium or sodium), improved the stability of catalyst, and accelerated the oxidation addition speed (the speed control step of reaction) of MeI to a certain extent; Reduced the water content in the Processes for Producing Acetic Acid simultaneously, wherein particularly remarkable with the promoting catalysis of lithium iodide.Effect through salt compounded of iodine can than obtain under the low water content with high water content under identical reactivity, improved the utilization ratio of CO.But produce in the catalystic converter system of acetic acid at the high iodine concentration of this type, possibly cause the concentration of residual iodine in the product acid higher, and then can for example cause poisoning of catalyst in the preparation of VAM in downstream product.
Except the alkali metal salt compounded of iodine; To other different types of catalytic promoters and transition metal salt Study of Stabilizers; Good progress is all arranged; Used the LiI stabilizing agent to be aided with the group vib slaine like US5218143, promptly adopting the acetate of lower valency molybdenum, chromium, tungsten or salt compounded of iodine is co-catalyst, or with Mo (CO)
6, W (CO)
6, Cr (CO)
6Carbonyls is a co-stabilizer, in the reaction of acetic acid synthesis from methanol carbonylation, has obtained result preferably.
Though the catalyst structure pattern in the existing suitability for industrialized production has catalytic activity preferably, when high temperature, low CO dividing potential drop, be prone to be converted into trivalent rhodium anionic complex, and then generate deposition and lose activity.In addition; Be to increase the dissolubility of catalyst in the production of acetic acid process, need reaction system to keep higher water and hydroiodic acid content so that the maintenance system high reaction activity and high (EP55618, EP161874); But therefore quickened water gas reaction; Consumed the raw material carbon monoxide, the severe corrosive of medium has improved the requirement to equipment material simultaneously, and the big water gaging that exists in the system has increased the complexity of product postprocessing operation.Catalyst system and catalyzing among the present invention has overcome some weakness of existing catalyst preferably.
Summary of the invention
The object of the present invention is to provide a kind of catalyst system and application thereof of synthesizing acetic acid by methanol low-pressure carbonylation, this system can be high-speed, highly selective is acetic acid with methanol conversion under lower temperature and pressure.Reaction has reduced the concentration of water and hydroiodic acid, and corrosion on Equipment property is reduced.
For realizing above-mentioned purpose; The catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation provided by the invention; As the activity of such catalysts thing, add alkyl iodide, water, hydroiodic acid, alkali metal salt compounded of iodine and sulfonate with rhodium salt, and be aided with polar solvent and form as co-catalyst; Wherein:
The consumption of rhodium salt is counted 200-1000ppm with rhodium by weight percentage;
The content of alkyl iodide in reaction system is 5%-18% by weight percentage;
The concentration of water is 4%-6% by weight percentage;
The concentration of hydroiodic acid is 0.2%-0.4% by weight percentage;
The concentration of alkali metal salt compounded of iodine is 7%-12% by weight percentage;
The mol ratio of sulfonate and rhodium salt is 1-100.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used rhodium salt is: RhCl
3, RhBr
3, RhI
3, Rh (OAc)
2, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2Or [Rh (CO)
2I]
2
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used alkyl iodide is an iodomethane.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used alkali metal salt compounded of iodine is a lithium iodide.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used sulfonate is Zn, ammonium and alkali-metal sulfonate.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used alkali metal sulfonate is LiHSO
3, NaHSO
3, KHSO
3Or their salt that contains the crystallization water.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, the used Zn or the sulfonate of ammonium are respectively Zn (HSO
3)
2, NH
4HSO
3Or their salt that contains the crystallization water.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, when catalyzed carbonylation prepared acetic acid, reactant was a methyl alcohol.
In the catalyst system of described synthesizing acetic acid by methanol low-pressure carbonylation, used polar solvent is an acetic acid, and its consumption is the 10-120% of reaction-ure mixture by weight.
When above-mentioned catalyst system provided by the invention is used in the synthetic preparation of low-pressure methanol carbonyl acetic acid; Carry out through in reactor, adding following ingredients: (I) methyl alcohol is as the raw material of reaction, (II) rhodium compound, (III) iodomethane, water, hydroiodic acid; (IV) lithium iodide; (V) sulfonate, (VI) acetate solvate, (VII) led to carbon monoxide.Reaction temperature is 160-190 ℃, and reaction pressure is 2.8-3.2MPa, and the reaction time is 0.1-0.5 hour.
The principal character of catalyst system provided by the invention is:
1, alkali metal salt compounded of iodine in this catalyst system and sulfonate all have stabilization to catalyst, make that the stability of catalyst is better, and operating mode scope applicatory is wideer, helps the adjustment and the optimization of production technology.
2, alkali metal salt compounded of iodine in this catalyst system and sulfonate are all benefited to improving activity of such catalysts.The dissolubility of lithium iodide in reaction medium is better, but too much lithium iodide can make the content of iodine in the system too high, and this follow-up iodine that removes for product has brought trouble.The addition of sulfonate in system is less relatively, but bigger to improving the activity of such catalysts contribution, this has alleviated the too high problem of content of iodine in the system to a certain extent.
3, reduced the concentration of water and hydroiodic acid in the reaction system, this separating technology for follow-up acetic acid and water provides great facility, and has reduced corrosion on Equipment.
4, this reaction system is under lower temperature and pressure, can be high-speed, highly selective is acetic acid with methanol conversion.
5, prepare in the reaction system of acetic acid in the catalyst carbonylation of methanol that the present invention relates to, acetic acid content is between the 10-120% (wt) of reaction medium.Acetic acid is a kind of excellent solvent; Can not only make in the reaction system chemofacies dissolubility between each main component can be better; And can increase the solubility of catalyst in reaction medium, also carbonylation is had and significantly induce and facilitation, so help the raising of rate of catalysis reaction.
6, prepare in the reaction system of acetic acid in the catalyst carbonylation of methanol that the present invention relates to, need not carry out the catalyst precarsor preliminary treatment of any complicacy, the formation of catalyst system and catalyzing is simple rapidly, catalytic process is convenient and easy.
The specific embodiment
Embodiment 1
In 250mL zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.150g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.10mol, water 4%, hydroiodic acid 0.2%, lithium iodide 8.0g, LiHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.0MPa, and the reaction time is 18min.Methanol conversion 99.0%, acetic acid space-time yield are 21.2molAcOH/ (Lh).
Embodiment 2
In 250mL zirconium matter autoclave pressure, add Rh (OAc)
20.160g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.12mol, water 4%, hydroiodic acid 0.3%, lithium iodide 8.0g, NaHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.2MPa, and the reaction time is 20min.Methanol conversion 99.1%, acetic acid space-time yield are 19.8molAcOH/ (Lh).
Embodiment 3
In 250mL zirconium matter autoclave pressure, add RhBr
30.330g, methyl alcohol 0.72mol, acetic acid 0.83mol, iodomethane 0.10mol, water 5%, hydroiodic acid 0.2%, lithium iodide 8.0g, LiHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.0MPa, and the reaction time is 21min.Methanol conversion 98.8%, acetic acid space-time yield are 18.5molAcOH/ (Lh).
Embodiment 4
In 250mL zirconium matter autoclave pressure, add [Rh (CO)
2I]
20.210g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.08mol, water 6%, hydroiodic acid 0.2%, lithium iodide 8.0g, NH
4HSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 2.8MPa, and the reaction time is 15min.Methanol conversion 99.0%, acetic acid space-time yield are 17.4molAcOH/ (Lh).
Embodiment 5
In 250mL zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.08mol, water 4%, hydroiodic acid 0.4%, lithium iodide 8.0g, KHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.2MPa, and the reaction time is 20min.Methanol conversion 99.0%, acetic acid space-time yield are 19.4molAcOH/ (Lh).
Embodiment 6
In 250mL zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.08mol, water 5%, hydroiodic acid 0.3%, lithium iodide 8.0g, LiHSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 2.8MPa, and the reaction time is 25min.Methanol conversion 99.1%, acetic acid space-time yield are 20.1molAcOH/ (Lh).
Embodiment 7
In 250mL zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.150g, methyl alcohol 0.79mol, acetic acid 0.83mol, iodomethane 0.10mol, water 5%, hydroiodic acid 0.4%, lithium iodide 8.0g, NH
4HSO
30.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.0MPa, and the reaction time is 18min.Methanol conversion 98.9%, acetic acid space-time yield are 17.2molAcOH/ (Lh).
Embodiment 8
In 250mL zirconium matter autoclave pressure, add RhI
30.330g, methyl alcohol 0.72mol, acetic acid 0.83mol, iodomethane 0.10mol, water 6%, hydroiodic acid 0.3%, lithium iodide 8.0g, Zn (HSO
3)
20.3g.
Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, 170 ℃ of reaction temperatures, reaction pressure keeps 3.0MPa, and the reaction time is 21min.Methanol conversion 98.8%, acetic acid space-time yield are 16.5molAcOH/ (Lh).
Claims (7)
1. the catalyst system of a synthesizing acetic acid by methanol low-pressure carbonylation as the activity of such catalysts thing, adds alkyl iodide, water, hydroiodic acid, alkali metal salt compounded of iodine and sulfonate as co-catalyst with rhodium salt, and is aided with polar solvent and forms, and it is characterized in that:
The consumption of rhodium salt is counted 200-1000ppm with rhodium by weight percentage;
The content of alkyl iodide in reaction system is 5%-18% by weight percentage;
The concentration of water is 4%-6% by weight percentage;
The concentration of hydroiodic acid is 0.2%-0.4% by weight percentage;
The concentration of alkali metal salt compounded of iodine is 7%-12% by weight percentage;
The mol ratio of sulfonate and rhodium salt is 1-100;
Said sulfonate is LiHSO
3, NaHSO
3, KHSO
3, Zn (HSO
3)
2, NH
4HSO
3Or their salt that contains the crystallization water.
2. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, used rhodium salt is: RhCl
3, RhBr
3, RhI
3, Rh (OAc)
2, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2Or [Rh (CO)
2I]
2
3. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, used alkyl iodide is an iodomethane.
4. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, used alkali metal salt compounded of iodine is a lithium iodide.
5. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, when catalyzed carbonylation prepared acetic acid, reactant was a methyl alcohol.
6. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, used polar solvent is an acetic acid, and its consumption is the 10-120% of reaction-ure mixture by weight.
7. the catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, when catalyzed carbonylation prepared acetic acid, reaction temperature was 160-190 ℃, and reaction pressure is 2.8-3.2MPa, and the reaction time is 0.1-0.5 hour.
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| CN1288124C (en) * | 2003-04-18 | 2006-12-06 | 上海吴泾化工有限公司 | Rhoaium/inorganic iodine compound catalyst system for reducing impurity in acetic acid production |
| CN100361746C (en) * | 2005-06-24 | 2008-01-16 | 上海焦化有限公司 | Thiazole sulfonate co-catalytic oxo-synthesis homogeneous rhodium catalyst and use thereof |
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